Hydroxycarbazole carboxylic acid arylamides



Patented Feb. 23, 1937 HYDROXYCARBAZOLE CARBOXYLIC ACID ARYLAMIDES Friedrich Muth, Leverkusen-I. G. Work, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application April 4, 1932, Serial 4 Claims.

The present invention relates to new hydroxycarbazole carboxylic acid arylamides, more particularly it relates to compounds which may be represented by the probable general formula:

In Great Britain September 21,

nitro group, an alkyl group, an alkoxy group, an aryloxy group and an acylamino group.

My new N-substituted 2-hydroxycarbazole-3- carboxylic acid arylamides are obtainable accord ing to the known methods generally used in the CO-NHR manufacture of compounds of this type, that means, by reacting with the corresponding aro- OH matic or heterocyclic amine upon the acid-chlo- I ride or an ester of the corresponding N-substi- R tuted 2-hydroxycarbazole-3-carboxylic acid, or [0 wherein R' stands for alkyl or for a hydrocarbon radical of the aromatic or aromaticaliphatic series, R" stands for an aromatic or heterocyclic nucleus, for example for a benzene,

by reacting with an arylester of isocyanic acid upon the free N-substituted hydroxycarbazole carboxylic acid, the best method of manufacture being more fully described in the following examnaphthalene, indole, carbazole, diphenylenoxide, ples- 15 fluorene and fluorenone nucleus, and wherein all The manufacture of the Startlng l bst tl ted nuclei may be Substituted by one or more mono- 2hydroxycarbazole-3-carboxy1ic acid has been valent substituents, such as halogen, the nitro described in my co-pending application 6 No. group an alkyl group, an acylamino gmup, an 584,010, filed December 30, 1931, entitled New alkoxy group, and an aryloxy group, but with hydroxycarbazole 9' 20 the exception of a group inducing solubility in My new llted 2-hydroXycarbazole-3- Water, such as the sulfonic acid group, the cap carboxylic acid arylamides are generally crystalboxylic acid group or a, hydroxy group For line white to grey substances, partially soluble example, in this formula the figure m may be in aqueous caustic alkalies, generally soluble in methyl, ethyl, propyl, butyl, isobutyl, benzyl alcoholic caustic alkalies, and are valuable inter- 25 chlorobenzyl, 3' 4' di h] b -1 4 nj t o,b l mediate products for the manufacture of azodyephenylethyl, phenyl, 2-methylpheny1,4-m 1;h 1 stuffs in substance, on a substratum or on the phenyl, 3-nitrophenyl, l-chlorophenyl, l-mefibre- I thoxyphenyl, naphthyl which is attached to the The mvenfilon 1S l r e by the fOHOWmg nitrogen atom .in ocor B-position, and the figure examples Wlthout bemg hmlted thereto: 30 m, may be an aromatic or heterocyclic nucleus Example 1.2l, 2 grams of 9-methyl-2-hyf the kind Stated above or also radical f the droxycarbazole-S-carboxylic acid and 12, 4 grams following types: of p-ohloroaniline are dissolved in 500 cos. of

toluene. At a temperature of 60-65" C. there are GO, dropped into the solution 10, 4 grams of phos- 5 phorus trichloride in the course of half an hour, while sirring, after this the temperature is raised C 'C to boiling in the course of 1 hour and kept for 8 hours at this temperature. The reaction mass 40 O-OOC is rendered alkaline by the addition of sodium 40 carbonate, any volatile compounds present are distilled off with steam, the precipitate is sucked off, while still warm, and washed with water. From pyridine the arylamide of the formula: 8 -CONH C1 i Q EH3 50 OSOz-O: is obtained in form of fine needles of themelting point 277 to 278 C. which may bear substituents as do not induce In an analogous manner there is obtained: solubility in water, for example, halogen, the 9-methy1-2-hydroxycarbazole 3-carboxylic acid- 5 anilide of the melting point 254 C., 9-methy1-2- hydroxycarbazole-3-oarboxylic acid-2'-anisidide of the melting point 188-190 C. and corresponding to the following formula:

Q-methyl-2-hydroxycarbazole-3-carboxylic acid 2-toluidide of the melting point 193 C., 9- methyl-2-hydroxycarbazole-3-carboxylic acid-2- methyl-4'methoxyanilide, 9-methyl-2-hydroxycarbazole-3-carboxylic acid-2'.5'-dimethoxyanilide, 9-'nethyl-2-hydroxycarbazole-3-carboxylic acid-l or 2-naphthylamide and 9-ethyl-2-hydroxycarbazole-3-carboxylic acid-2'-toluidide of the melting point 187 C. and corresponding to the following formula:

Example 2.12, 9 grams of Q-methyl-Z-hydroxycarbazole-3-carboxylic acid and 10 grams of l-aminocarbazole are dissolved in 500 cos. of dimethylaniline. At a temperature of 60-65 C., 5.5 grams of phosphorus trichloride are slowly dropped in, and after this, the reaction mass is slowly heated to 125-130 C. and kept at this temperature for 8 hours. The dimethylaniline is then distilled off with steam, and the residue is purified by successively boiling with aqueous sodium carbonate solution, aqueous caustic soda lye and aqueous hydrochloric acid. The arylide of the formula:

| CHa droxycarbazole 3-carboxylic acid and o-toluidine has the melting point of 135 C., it is scarcely soluble in aqueous caustic alkalies, soluble in alcoholic caustic alkalies.

The aryla-mides with aminocarbazoles, diphenyleneoxides, fluorenes or fiuorenones are high melting, greyish powders, soluble in alcoholic caustic alkalies.

I claim:

1. Hydroxycarbazole carboxylic acid arylamides of the general formula:

-o ONH-R \N -OH wherein R. stands for a member selected from the group consisting of: alkyl, aralkyl, a. radical of the benzene series and a radical of the naphthalene series, and R stands for a member selected from the group consisting of a radical of the benzene-, naphthalene-, carbazoleand indole series, being generally white to grey, crystalline substances, partially soluble in aqueous caustic alkalies, generally soluble in alcoholic caustic alkalies and being valuable intermediate products for the manufacture of azodyestufis in substance, on a substratum or on the fibre.

2. The arylamide of the following formula:

being a crystalline substance of the melting point 277-278 C. and being a valuable intermediate product for the manufacture of azodyestufis in substance, on a substratum or on the fibre.

3. Q-methyl -2- hydroxycarbazole -3- carboxylic acid-2-anisidide of the formula:

being a crystalline substance of the melting point 188-190 C. and being a valuable intermediate product for the manufacture of azodyestufis in substance, on a substratum or on the fibre.

4. 9 ethyl -2- hydroxycarbazole 3- carboxylic acid-'2-toluidide of the formula:

(IJ2H5 being a crystalline substance of the melting point 187 C. and being a valuable intermediate product for the manufacture of azodyestuifs in substance, on a substratum or on the fibre.

FRIEDRICH MUTH. 

